Process of manufacturing concentrated aqueous emulsions and emulsions produced by such process



United States Patent 01 3,455,178 Patented Sept. 9, 1969 PROCESS OFMANUFACTURING CONCENTRATED AQUEOUS EMULSIONS AND EMULSIONS PRO- ]DUCEDBY SUCH PROCFASS Heinz Enders, Stadtbergen, near Augsburg, and HansDiener, Neusaess-Lowald, near Augsburg, Germany, assignors to ChemischeFabrik Pfersee G.m.b.H., Augsburg, Germany No Drawing. Filed Dec. 28,1965, Ser. No. 517,081 Claims priority, application Germany, Jan. 16,1965,

C 34,872; May 7, 1965, C 35,781 Int. Cl. C09k 3/18; C09d 5/20; D06m /66US. Cl. 106-2 9 Claims ABSTRACT OF THE DISCLOSURE An emulsion suitable,when diluted, for the hydrophobing of fibrous materials is produced byemulsifying a liquefied water-insoluble wax, fat or silicones with asalt mixture expressed as oxides in aqueous solution and consisting ofsalts of titanium and zirconium with a monocarboxylic acid with 1 to 4carbon atoms in a weight ratio when expressed as titanium oxide andzirconium oxide as ranging between 1:0.6 to 1:3, the weight ratiobetween emulsified substances and metal salts calculated as oxides beingbetween about 120.1 and about 1:03.

This invention relates to a process of manufacturing concentratedaqueous emulsions and to emulsions which are produced by such processand which are particularly suitable, when diluted, for the hydrophobingof fibrous materials.

As far as prior art is concerned, German Patent No. 908,052 describes aprocess of emulsifying paraffin hydrocarbons, waxes or fats with aqueoussolutions of basic aluminum salts, whereby the fats either have an acidvalue or must be mixed to the extent of about 10% by weight with fattyor waxy acids. These emulsions serve essentially for making textiles andother fibrous materials water-repellent. However, they do not resistwashing.

German Patent No. 749,740 describes the use of salts of fourvalentmetals, such as zirconium, to produce emulsions which have substantiallybetter wash-resistant hydrophobic effects. It was also suggested to usesalts of other fourvalent metals, such as titanium, but such use did notmaterialize in actual practice, since they have drawbacks which will beset forth hereinafter.

A suggestion has also been made to replace partly the expensive salts offourvalent metals, such as those of zirconium, by basic aluminum salts.However, results obtained with such emulsions, as well as theirwash-resistance, are rather poor.

German specification No. 1,052,943 discloses emulsification of siliconsin the same manner with the addition of about 10 to by weight of higherfatty acids, with concentrated aqueous solutions of basic salts ofaluminum and/or zirconium, and the use of the emulsions forwaterrepellent impregnation. However, when only basic aluminum salts areused for the formation of the emulsion, wash-resistance is very poor; itis only slightly improved when mixtures of zirconium and aluminum saltsare used. Wash resistance is much better when basic zirconium salts areused. Practical experimentation has shown that particularly goodwater-repellent and wash-resistant effects are produced by emulsionsobtained from basic titanium salts. They have various drawbacks,however.

This literature indicates that it is known in prior art to produceemulsions of paraffins or organopolysiloxanes with the use of 3 or4-valent metal salts, including those of aluminum and zirconium, as wellas titanium, in the presence or in the absence of about 10% of higherfatty acids. These emulsions can make fabrics water repellent. Wash andcleaning resistance produced by the coatings is less with aluminum,greater with zirconium and is still better with titanium salts.

It should be noted, however, that water-repellent impregnation is oftencombined with treatments by synthetic resin pre-condensates andhardening agents. To avoid the danger of a fishy smell in the material,salts of two-valent metals, such as chlorides or nitrates of magnesiumor zinc are preferred as hardening agents to ammonium salts. Practicalexperimentation has shown, however, that emulsions produced withtitanium salts have the drawback that they are incompatible with saltsof two-valent metals and produced deposits in the treating baths. Theircombination with synthetic resins, which is generally used inhydrophobing, is possible only in a very limited manner, namely withamine salt catalysts.

In addition, as far as silicon emulsions are concerned, the resultanteffects depend not only upon the type of the basic salt but also uponthat of the silicon. Hydropolysiloxanes produce good results, whilesilicons without a splittable hydrogen atom produce only mediocreresults which do not rise to the modern requirements, even if theemulsification takes place solely with basic zirconium or titaniumsalts.

An object of the present invention is to eliminate these drawbacks ofprior art processes and emulsions.

Another object is to produce with the use of specific mixtures oftitanium and zirconium salts, emulsions which when applied to fabricswill impart to them excellent wash resistance (at least as good as thatproduced with titanium salt alone) and which at the same time can becombined with metal salt catalysts.

Other objects of the present invention will become apparent in thecourse of the following specification.

The present invention is based in part on the surprising discovery thatemulsions can be produced, the effects of which will be as good as thoseobtained with titanium salts alone, and which will not have theabove-mentioned drawbacks, when aqueous solutions of salts of titaniumand zirconium with monocarboxylic acids with 1-4 carbon atoms in a ratioby weight of 1 titanium oxide to 0.6-3.0 zirconium oxide are used foremulsifying water insoluble substances, such as waxes, paraflin, fats orsilicones. Acetic acid is the preferred choice among salt-formingmonocarboxylic acids with 1 to 4 carbon atoms, while the preferredWeight ratio of titanium oxide to zirconium oxide is 1:13.

It is possible to use quaternary as well as basic salts of titanium orzirconium. The two salts can be dissolved in water separately or as amixture. The aqueous solution can be buffered to a pH value of about 4.5by the addi tion of alkali salts or ammonium salts of weak acids, suchas those of acetates, carbonates or bicarbonates, or it can be convertedinto a solution of a mixture of basic salts. It can be also produced bydissolving the alcoholates of titanium and zirconium with low monovalentalcohols in water and the addition of an under-stoichiometric amount ofthe low monocarboxylic acid, especially acetic acid.

The emulsions of the present invention are produced in theirconcentrated condition, i.e. they contain about 25 percent by weight, ormore, of nonaqueous substances and when used technically they arediluted with several times their quantities of water. The weight ratiobetween emulsified substances and metal salts (calculated as oxides)lies between about 110.1 and about 110.3, particularly at 110.2.

The emulsions of the different substances can be also produced withoutthe use of 120% aliphatic monocarboxylic acid with at least 12 C-atoms.In all instances it is possible to additionally emulsify organicsolvents.

When the emulsions of the present invention are used for making textilesand other fibrous materials waterrepellent, their advantages are thatthey produce very good results and that the treated materials haveexcellent stability against chemical cleaning and washing with soap. Theresults are better than those produced by emulsions made solely withzirconium salts. As compared to emulsions made solely from titaniumsalts, they have the advantage that they produce stable treating bathswith salts of two-valent metals, which are used as hardening agents forsynthetic resin precondensates. With reference to silicone emulsionsthere is the additional advantage that very good results are producedeven when an organopolysiloxane is emulsified which does not have asplittable hydrogen atom.

When organopolysiloxanes are emulsified in accordance with the processof the present invention, they can be indicated by the general formulawherein R or R are hydrogen, an alkyl, aryl, cycloalkyl, or acylresidue, x+y is a number between 1.5 and 3 and n is a number higher than1.

The following examples are given by way of illustration only:

EXAMPLE 1 80 kg. technical zirconium tetraacetate (35-37% ZrO aredissolved in 550 1. water and 80 kg. titanium tetraacetate (26% TiO areadded while stirring to the solution. A warm solution of 6070 C. is thusproduced. 20 kg. lignite wax acid (acid number 135; melting point 80 C.)molten in 170 kg. paraflin (M.P. 5055) are slowly added in a turbornixerto the solution. After adding 260 1. water the resulting product iscirculated through a homogenizing machine and is cooled while thestirring is continued. A very fine-particled liquid emulsion is producedwhich keeps very well in storage.

A hath made from this emulsion produces upon textiles the same excellentwater-repellent effects as an emulsion made only with titaniumtetraacetate, but contrary to the latter, it remains completely stablewith salts of two-valent metals which are used as hardening catalystsjointly with heat-hardening synthetic resin precondensates.

EXAMPLE 2 50 kg. titanium tetraacetate are dissolved along with 30 kg.zirconium tetraacetate in 250 1. water. After heating to 6070 C. anothersolution is added in a turbomixer which has also been brought to 60 C.and which consists of 84 kg. parafiin (M.P. 50-55 3.5 technical stearicacid (A.N. 206, M.P. 65) and 7.5 kg. lignite Wax acid (A.N. 90, M.P. 80)in 101. benzene (boiling point about 120 to 140 C.). After adding 60 1.water the resulting product is advantageously additionally homogenized.

The emulsion consists of very fine particles and can be diluted withwater in any proportion. When diluted it is compatible in an excellentmanner with synthetic resin precondensates and their metal saltcatalysts and when used by itself or in combination with syntheticresins it produces better hydrophobic effects than a correspondingemulsion made with zirconium salt.

EXAMPLE 3 60 kg. zirconium tetraacetate are dissolved in 400 1. waterand 25 kg. ammonium acetate are added. Immediately thereafter 30 kg.titanium tetraacetate are dissolved therein, the solution is heated to60-70 C. and a liquefied mixture of 170 kg. paraffin (M.P. 60 C.) and 30kg. lignite wax acid (A.N. 135, M.P. 80) is introduced with forcefulstirring. After adding 300 1. water the emulsion is homogenized andstirred until cool. Instead of the acetates equivalent amounts offormiates may be used. The emulsions thus produced have propertiessimilar to those set forth in the preceding examples.

4 EXAMPLE 4 55 kg. zirconium tetraacetate, 27 kg. ammonium bicarbonateand 50 kg. titanium tetraacetate are dissolved in 388 1. water at 60 C.A solution is stirred into it with the use of a quick stirrer,consisting of 250 kg. dimethyl siloxane (viscosity 750 cst., SiO contentand 25 kg. oleic acid mixed with 36 kg. perchloroethylene and 114 kg.toluene; the emulsion which is thus produced is diluted with 520 1.water and finally is homogenized in a high pressure machine.

This emulsion consists of fine particles, keeps Well in storage and canbe easily diluted with water. When used for the water repellentimpregnation of textiles, very good results are obtained, which can notbe produced by an emulsion made solely from basic zirconium acetate.

EXAMPLE 5 In the same manner and with the same relative amounts 250 kg.methyl hydrosiloxane with a SiO content of 99% can be transformed into avery good emulsion.

EXAMPLE 6 35 kg. zirconium tetraformiate (about 44% ZrO are dissolved in270 1. water while heating to 60 to 70 C., then 27 kg. ammoniumbicarbonate and finally 50 kg. technical titanium tetraformiate (about40% TiO are dissolved; with the use of a centrifugal mixer 80 kg. of amethyl hydrosiloxane are stirred in, which is blocked endwise byphenyl-diethylsiloxy groups, with a viscosity of 100 cst. at 25 C., andwhich is mixed with 10 kg. molten stearic acid; the preemulsion which isthus produced is diluted with 80 1. Warm water and finally homogenized.This emulsion is also stable and when diluted produces good waterrepellent effects which withstand cleaning.

EXAMPLE 7 37 kg. titanium tetraacetate (26% TiO 75 kg. zirconiumtetraacetate (36% ZrO and 31 kg. ammonium acetate are dissolved in 500l. warm water; a molten mixture is stirred in, consisting of 200 kg. ofa liquid mixed polymer (viscosity 350 cst.) composed of diandtrirncthylsiloxane units, and 20 kg. mineral wax (acidity 90). Afterhomogenizing a fine-particled stable emulsion is formed, which has verygood water-repellent effects similar in extent to those of an emulsionproduced from methylhydrosiloxane and basic zirconium salts, but havinga better resistance against washing.

EXAMPLE 8 kg. of an aqueous zirconium acetate solution (26% zirconiumoxide and 43% acetic acid) are mixed with 117 kg. of an aqueous titaniumacetate solution (17% titanium dioxide and 45% acetic acid) and arediluted with a solution of 48 kg. urea and 5 kg. ammonium bicarbonate in550 1. water. To this solution which is maintained at 60 C. are slowlystirred in by the use of a quick stirrer kg. paraffin (melting point 58to 60) which have been heated to 80 to 90 C. The emulsion which is thusproduced is diluted with 210 1. Warm water of 60 C. and is finallyhomogenized. This emulsion is very stable in concentrated as well asdiluted state and produces better water-repellent effects upon a cottonfabric than an emulsion made only from a zirconium salt. Itscompatibility with magnesium salts or similar salts of two-valentmetals, which are used jointly with synthetic resin precondensates ashardening means, is very good.

EXAMPLE 9 A very useful emulsion can be produced under the sameconditions and with the same relative amounts as set forth in Example 4,but leaving out 25 kg. oleic acid. The properties of such emulsion areto a great extent the same as those of the emulsion which was made withthe addition of oleic acid.

It is apparent that the above examples have been given solely by way ofillustration and not by way of limitation and that they are capable ofmany variations and modifications within the scope of the presentinvention. All such variations and modifications are to be included inthe scope of the present invention.

What is claimed is:

1. For hydrophobing fibrous materials, a diluted emulsion produced byemulsifying a liquefied water-insoluble substance selected from theclass consisting of waxes, solid to liquid natural and synthetic fatsand silicones with an aqueous .solution of salts of titanium andzirconium mixed in a weight ratio when expressed as titanium oxide andzirconium oxide as ranging between 1:06 to 1:3 with a monocarboxylicacid with l to 4 carbon atoms, the weight ratio between the emulsifiedsubstance and metal salts calculated as oxides being substantiallybetween 1:0.l and 1:0.3.

2. A process of manufacturing concentrated aqueous acid-reactingemulsions, which comprises emulsifying of a liquefied water-insolublesubstance selected from the class consisting of waxes, solid to liquidnatural and synthetic fats and silicones with a salt mixture expressedas oxides in aqueous solution, wherein said salt mixture consists ofsalts of titanium and zirconium with a monocarboxylic acid with 1 to 4carbon atoms in a weight ratio when expressed as titanium oxide andzirconium oxide as ranging between 1:06 to 1:3, the weight ratio betweenthe emulsified substance and metal salts calculated as oxides beingsubstantially between 110.1 and 1:0.3.

3. The process in accordance with claim 2, wherein the salts of titaniumand zirconium are quaternary salts.

4. The process in accordance with claim 2, wherein the salts of titaniumand zirconium are basic salts.

S. The process in accordance with claim 2, wherein the mono-carboxylicacid with l to 4 carbon atoms is acetic acid.

6. The process in accordance with claim 2, wherein the weight ratio is ltitanium oxide to 1.3 zirconium oxide.

7. The process in accordance with claim 2, further comprisingemulsifying at least one organic solvent for the water-insolublesubstance.

8. The process in accordance with claim 2, further comprisingemulsifying an aliphatic monocarboxylic acid with substantially 12 to 26carbon atoms in an amount of 10 to 20 percent of the weight of thewater-insoluble substance.

9. The process in accordance with claim 2, wherein the wax is aparaflin.

References Cited UNITED STATES PATENTS 2,345,142 3/1944 Muller 106-271XR 2,350,800 6/1944 Muller 106271 XR 2,402,351 6/1946 Smith et al.106271 XR 2,635,055 4/1953 Figdor 106271 JULIUS FROME, Primary ExaminerL. HAYES, Assistant Examiner US. Cl. X.R.

